CN106939143A - The preparation method of photocuring aqueous polyurethane silica silicon inierpeneirating network structure coating material - Google Patents
The preparation method of photocuring aqueous polyurethane silica silicon inierpeneirating network structure coating material Download PDFInfo
- Publication number
- CN106939143A CN106939143A CN201710160316.0A CN201710160316A CN106939143A CN 106939143 A CN106939143 A CN 106939143A CN 201710160316 A CN201710160316 A CN 201710160316A CN 106939143 A CN106939143 A CN 106939143A
- Authority
- CN
- China
- Prior art keywords
- silicon
- coating material
- aqueous polyurethane
- network structure
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title claims abstract description 15
- 238000000016 photochemical curing Methods 0.000 title claims abstract 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000377 silicon dioxide Substances 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000839 emulsion Substances 0.000 claims abstract description 23
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000009833 condensation Methods 0.000 claims abstract description 12
- 230000005494 condensation Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 150000002009 diols Chemical class 0.000 claims description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 238000012643 polycondensation polymerization Methods 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 12
- 235000019260 propionic acid Nutrition 0.000 claims 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 6
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims 1
- -1 dihydroxymethyl Chemical group 0.000 claims 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 25
- 239000002243 precursor Substances 0.000 description 13
- 239000012975 dibutyltin dilaurate Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004762 orthosilicates Chemical class 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
技术领域technical field
本发明属于水性光固化有机-无机涂层材料的制备技术领域。The invention belongs to the technical field of preparation of water-based photocurable organic-inorganic coating materials.
背景技术Background technique
随着我国对环境保护的重视，环保立法日益完善，人们对环境保护的呼声越来越高，对涂料中VOC排放进行严格控制。水性聚氨酯光固化涂层材料具有高效、节能、环保、安全卫生等优点，并广泛应用于纸张上光油、木器清漆、丝印油墨、电沉积光致抗蚀剂等领域。但其涂层的力学性能、耐水性、耐热性及表面疏水性还远远达不到传统的油性光固化聚氨酯， 所以，如何改善光固化水性聚氨酯的性能已成为水性聚氨酯涂层材料发展的主要方向之一，光固化水性涂料技术因其施工效率高以及环保优势日益为人们所关注。With the emphasis on environmental protection in our country, environmental protection legislation is becoming more and more perfect, people's voice for environmental protection is getting higher and higher, and VOC emissions in coatings are strictly controlled. Water-based polyurethane light-curing coating materials have the advantages of high efficiency, energy saving, environmental protection, safety and hygiene, and are widely used in paper varnishes, wood varnishes, screen printing inks, electrodeposition photoresists and other fields. However, the mechanical properties, water resistance, heat resistance and surface hydrophobicity of the coating are far from the traditional oil-based light-cured polyurethane. Therefore, how to improve the performance of light-cured water-based polyurethane has become the development of water-based polyurethane coating materials. One of the main directions, light-curing water-based coating technology has attracted increasing attention due to its high construction efficiency and environmental protection advantages.
光固化水性聚氨酯主要由基料树脂、光引发剂和助剂组成。固化涂层的性能主要由基料树脂的结构特点决定。光固化的水性聚氨酯的基料树脂包含可进行光固化活性基团如双键和可成盐的基团。因此，光固化活性基团含量及光活性、聚氨酯软硬段结构与相对比例、成盐后亲水基团的含量均对光固化水性聚氨酯材料的综合性能起着重要的影响。然而，水性聚氨酯中光固化活性基团含量低，导致涂层交联密度低，涂层硬度差，光泽低，耐醇性差；同时由于大量亲水基团不可避免地带来涂层耐水性差的问题，难以满足应用过程中对涂层提出的越来越高的性能要求。Photocurable waterborne polyurethane is mainly composed of base resin, photoinitiator and additives. The performance of the cured coating is mainly determined by the structural characteristics of the base resin. The base resin of photocurable waterborne polyurethane contains photocurable active groups such as double bonds and salt-forming groups. Therefore, the content and photoactivity of photocurable active groups, the structure and relative proportion of soft and hard segments of polyurethane, and the content of hydrophilic groups after salt formation all play an important role in the comprehensive performance of photocurable waterborne polyurethane materials. However, the content of photocurable active groups in waterborne polyurethane is low, resulting in low crosslinking density of the coating, poor coating hardness, low gloss, and poor alcohol resistance; at the same time, due to a large number of hydrophilic groups, the problem of poor water resistance of the coating is inevitable , it is difficult to meet the increasingly higher performance requirements for coatings in the application process.
发明内容Contents of the invention
针对现有光固化水性聚氨酯涂层材料存在硬度低、光泽不高，耐醇性差以及耐水性差的缺点，提出一种光固化水性聚氨酯-硅-氧-硅互穿网络结构涂层材料的制备方法。Aiming at the shortcomings of existing light-cured waterborne polyurethane coating materials, such as low hardness, low gloss, poor alcohol resistance and poor water resistance, a preparation method of light-cured waterborne polyurethane-silicon-oxygen-silicon interpenetrating network structure coating material is proposed .
本发明技术方案包括以下步骤：Technical scheme of the present invention comprises the following steps:
1）将二异氰酸酯、聚酯二元醇、二羟甲基丙酸 (DMPA)和二月桂酸二丁基锡混合，在混合体系的温度为75～80℃的条件下反应制得预聚体；1) Mix diisocyanate, polyester diol, dimethylolpropionic acid (DMPA) and dibutyltin dilaurate, and react at a temperature of 75-80°C to prepare a prepolymer;
2）将预聚体和含羟基的丙烯酸树脂混合，在70～75℃的条件下反应至结束后，降温至40℃后，加入三乙胺进行中和反应，中和反应结束后再加去离子水乳化，得到可UV光固化水性聚氨酯乳液；2) Mix the prepolymer and hydroxyl-containing acrylic resin, react at 70-75°C until the end, cool down to 40°C, add triethylamine for neutralization reaction, and then remove Emulsified with ionic water to obtain UV-curable water-based polyurethane emulsion;
3）将所述可UV光固化水性聚氨酯乳液和有机硅改性正硅酸乙酯预缩合前驱体混合，经UV光固化及缩合聚合，得到光固化水性聚氨酯-硅-氧-硅互穿网络结构涂层材料。3) Mix the UV-curable water-based polyurethane emulsion with the silicone-modified tetraethyl orthosilicate pre-condensation precursor, and undergo UV light-curing and condensation polymerization to obtain a photo-curable water-based polyurethane-silicon-oxygen-silicon interpenetrating network Structural coating materials.
本发明首先制备可与有机硅改性正硅酸乙酯预缩合前驱体相容，并且可UV的光固化水性聚氨酯乳液，然后再将可UV光固化水性聚氨酯乳液与有机硅改性正硅酸乙酯预缩合前驱体混合制备得到光固化水性聚氨酯-硅-氧-硅互穿网络结构涂层材料。可UV光固化水性聚氨酯乳液与有机硅改性正硅酸乙酯预缩合前驱体相容的特征，即两者混合时不产生沉淀或粘度增大等现象，两者在混合成膜过程中，有机硅可以与水性聚氨酯疏水链发生疏水相互作用，在UV光固化过程中有机硅改性正硅酸乙酯预缩合前驱体随分散介质的挥发而发生缩合聚合反应，最终形成聚合物与Si-O-Si互穿网络结构有机-无机杂化涂层材料。本发明得到的涂层材料具有优良的硬度，光泽，附着力、韧性以及耐水性等，解决了水性聚氨酯耐水性差及光泽低的弊端。The present invention firstly prepares a UV light-curable water-based polyurethane emulsion that is compatible with the pre-condensed precursor of organosilicon-modified orthosilicate, and then combines the UV light-curable water-based polyurethane emulsion with organosilicon-modified orthosilicate The photocurable waterborne polyurethane-silicon-oxygen-silicon interpenetrating network structure coating material was prepared by mixing ethyl ester precondensed precursors. UV light-curable water-based polyurethane emulsion is compatible with silicone-modified tetraethyl orthosilicate pre-condensed precursor, that is, when the two are mixed, there will be no precipitation or viscosity increase. During the process of mixing the two, Silicone can interact hydrophobically with the hydrophobic chain of waterborne polyurethane. During the UV light curing process, the pre-condensed precursor of silicone-modified tetraethyl orthosilicate undergoes condensation polymerization reaction with the volatilization of the dispersion medium, and finally forms a polymer and Si- O-Si interpenetrating network structure organic-inorganic hybrid coating material. The coating material obtained by the invention has excellent hardness, gloss, adhesion, toughness, water resistance, etc., and solves the disadvantages of poor water resistance and low gloss of the water-based polyurethane.
本发明的关键技术及有益效果：（1）以水代替传统的溶剂为介质，减少了VOC的排放，减少了对环境的污染。（2）设计有机-无机互穿网络交联结构来提高水性UV光固化聚氨酯涂层的交联密度，从而解决现有水性聚氨酯普遍存在的硬度低、光泽不高、耐醇擦洗性差、不耐水的弊端。Key technologies and beneficial effects of the present invention: (1) Using water instead of traditional solvents as the medium reduces VOC emissions and environmental pollution. (2) Design the organic-inorganic interpenetrating network cross-linking structure to increase the cross-linking density of water-based UV light-cured polyurethane coatings, so as to solve the common problems of existing water-based polyurethanes such as low hardness, low gloss, poor alcohol scrub resistance, and water resistance disadvantages.
进一步地，本发明所述聚酯二元醇与二羟甲基丙酸的总量与二异氰酸酯的摩尔比为1∶1.4～1.75，且，二羟甲基丙酸占二异氰酸酯、聚酯二元醇、二羟甲基丙酸 (DMPA)和二月桂酸二丁基锡的混合总质量的4%～6%，二月桂酸二丁基锡占二异氰酸酯、聚酯二元醇、二羟甲基丙酸 (DMPA)和二月桂酸二丁基锡的混合总质量的0.1～0.2%。亲水扩链剂二羟甲基丙酸在此比例可以使得水性聚氨酯乳液稳定，催化剂二月桂酸二丁基锡可以使反应较为平稳。Further, the molar ratio of the total amount of polyester diol and dimethylol propionic acid to diisocyanate in the present invention is 1:1.4～1.75, and dimethylol propionic acid accounts for diisocyanate, polyester diisocyanate 4% to 6% of the total mass of alcohol, dimethylol propionic acid (DMPA) and dibutyltin dilaurate, dibutyltin dilaurate accounts for diisocyanate, polyester diol, dimethylolpropionic acid (DMPA) and dibutyltin dilaurate mixed total mass of 0.1 to 0.2%. The ratio of the hydrophilic chain extender dimethylolpropionic acid can make the water-based polyurethane emulsion stable, and the catalyst dibutyltin dilaurate can make the reaction more stable.
所述步骤1）中，所述二异氰酸酯为六亚甲基二异氰酸酯或异佛尔酮二异氰酸酯中任意一种。六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯均是脂肪族二异氰酸酯，具有较好的耐黄变性，合成的水性聚氨酯不易泛黄。In the step 1), the diisocyanate is any one of hexamethylene diisocyanate or isophorone diisocyanate. Both hexamethylene diisocyanate and isophorone diisocyanate are aliphatic diisocyanates with good yellowing resistance, and the synthesized water-based polyurethane is not easy to yellow.
所述聚酯二元醇为聚己内酯二元醇。采用聚己内酯二元醇合成的水性聚氨酯的耐温和耐水性都比较好。The polyester diol is polycaprolactone diol. The waterborne polyurethane synthesized by polycaprolactone diol has better temperature and water resistance.
所述含羟基的丙烯酸树脂为丙烯酸羟乙酯、丙烯酸羟丙酯或季戊四醇三丙烯酸酯中任意一种。含羟基的丙烯酸树脂既提供了羟基可以与异氰酸根反应，又含有活性双键可进行UV光固化。The hydroxyl-containing acrylic resin is any one of hydroxyethyl acrylate, hydroxypropyl acrylate or pentaerythritol triacrylate. The hydroxyl-containing acrylic resin not only provides hydroxyl groups that can react with isocyanate groups, but also contains active double bonds for UV light curing.
所述步骤2）中，所述羟基的丙烯酸树脂的摩尔量与预聚体中NCO的摩尔量的投料比为0.1～0.6∶1，可以对-NCO进行完全封端，并提供了理想的活性双键含量。In the step 2), the feed ratio of the molar amount of the hydroxyl acrylic resin to the molar amount of NCO in the prepolymer is 0.1-0.6:1, which can completely block the -NCO and provide ideal activity double bond content.
所述步骤2）中，加入三乙胺的摩尔量与二羟甲基丙酸的摩尔量相同。当三乙胺过量或不足时，均会使得水性聚氨酯的储存稳定性下降。In the step 2), the molar amount of triethylamine added is the same as that of dimethylol propionic acid. When triethylamine is excessive or insufficient, the storage stability of waterborne polyurethane will decrease.
所述可UV光固化水性聚氨酯乳液和有机硅改性正硅酸乙酯预缩合前驱体的混合质量比为1∶1.5～3，此比例下，漆膜的硬度、光泽等综合性能优异，可UV光固化水性聚氨酯乳液过多，使得漆膜的光泽度不够，可UV光固化水性聚氨酯乳液过少，漆膜的柔韧性不好。The mixing mass ratio of the UV-curable water-based polyurethane emulsion and the silicone-modified tetraethyl orthosilicate pre-condensation precursor is 1:1.5-3. Under this ratio, the comprehensive properties such as hardness and gloss of the paint film are excellent, and can be Too much UV light-curable water-based polyurethane emulsion leads to insufficient gloss of the paint film, and too little UV light-curable water-based polyurethane emulsion leads to poor flexibility of the paint film.
具体实施方式detailed description
实施例1：Example 1:
1、可光固化水性聚氨酯乳液的制备：1. Preparation of photocurable water-based polyurethane emulsion:
将40.0g(0.24mol)六亚甲基二异氰酸酯(HDI)、58.0g(0.11mol) PCL205u（聚己内酯二元醇）、4.0g(0.027mol)二羟甲基丙酸 (DMPA) 、0.2g二月桂酸二丁基锡，在75℃反应4h，制备预聚体。此时PCL205u和 DMPA的总量与HDI的投料摩尔比为1∶1.75，二羟甲基丙酸占用于制备预聚体的原料总质量的4%，二月桂酸二丁基锡占用于制备预聚体的原料总质量的0.2%。40.0g (0.24mol) hexamethylene diisocyanate (HDI), 58.0g (0.11mol) PCL205u (polycaprolactone diol), 4.0g (0.027mol) dimethylolpropionic acid (DMPA), 0.2g of dibutyltin dilaurate was reacted at 75°C for 4h to prepare a prepolymer. At this time, the molar ratio of the total amount of PCL205u and DMPA to HDI was 1:1.75, dimethylolpropionic acid accounted for 4% of the total mass of raw materials used to prepare the prepolymer, and dibutyltin dilaurate accounted for 4% of the total mass of raw materials used to prepare the prepolymer. 0.2% of the total mass of raw materials.
向预聚体中加入16.6g(0.14mol)丙烯酸羟乙酯，70℃反应2h，对预聚体的-NCO 进行封端。此时，丙烯酸羟乙酯的摩尔量与预聚体中NCO的摩尔量的投料比为0.6∶1。 降温至40℃，加入2.7g(0..027mol)三乙胺进行中和反应10min生成盐。其中三乙胺的摩尔量与DMPA 的摩尔量相同。 加入去离子水进行乳化 15min，得到可光固化水性聚氨酯乳液。Add 16.6 g (0.14 mol) of hydroxyethyl acrylate to the prepolymer, react at 70°C for 2 hours, and end-cap the -NCO of the prepolymer. At this time, the feed ratio of the molar amount of hydroxyethyl acrylate to the molar amount of NCO in the prepolymer is 0.6:1. Cool down to 40°C, add 2.7g (0..027mol) triethylamine to carry out neutralization reaction for 10min to generate salt. Wherein the molar weight of triethylamine is the same as that of DMPA. Deionized water was added for emulsification for 15 minutes to obtain a photocurable water-based polyurethane emulsion.
2、有机硅改性正硅酸乙酯预缩合前驱体的制备：2. Preparation of organosilicon-modified ethyl orthosilicate pre-condensation precursor:
将7.7g正硅酸乙酯（TEOS）、0.545g γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570）、1g水、3.4g乙醇混合，以盐酸调整混合体系的pH至6后，于60℃反应6h，得到有机硅改性正硅酸乙酯预缩合前驱体。Mix 7.7g tetraethyl orthosilicate (TEOS), 0.545g γ-methacryloxypropyl trimethoxysilane (KH570), 1g water, 3.4g ethanol, adjust the pH of the mixed system to 6 with hydrochloric acid , and reacted at 60°C for 6h to obtain a pre-condensed precursor of organosilicon-modified ethyl orthosilicate.
3、涂层材料的制备：3. Preparation of coating materials:
将可光固化水性聚氨酯乳液与有机硅改性正硅酸乙酯预缩合前驱体按质量比为1∶1.5的比例混合，进行UV光固化及进一步缩合聚合后，得到涂层材料。The photocurable water-based polyurethane emulsion is mixed with the organosilicon-modified tetraethyl orthosilicate pre-condensation precursor in a mass ratio of 1:1.5, and after UV light curing and further condensation polymerization, the coating material is obtained.
4、验证产品性能：4. Verify product performance:
将取得的涂层材料，按照GB/T 1743-1979进行光泽度测试，得到涂层光泽度92o；The obtained coating material is subjected to a gloss test according to GB/T 1743-1979, and the coating gloss is 92 ° ;
按照GB 1720-1979进行附着力检测，附着力1级。Adhesion test according to GB 1720-1979, adhesion level 1.
按照GB/T 6739-1996进行硬度检测，硬度为2H。The hardness test is carried out according to GB/T 6739-1996, and the hardness is 2H.
实施例2：Example 2:
1、可光固化水性聚氨酯乳液的制备：1. Preparation of photocurable water-based polyurethane emulsion:
将52.0g(0.23mol)异佛尔酮二异氰酸酯(IPDI)、58.0g(0.11mol) PCL205u（聚己内酯二元醇）、7.0g(0.047mol)二羟甲基丙酸 (DMPA) 、0.16g二月桂酸二丁基锡，在75℃反应4h，制备预聚体。此时PCL205u和 DMPA的总量与IPDI的投料摩尔比为1∶1.465，二羟甲基丙酸占用于制备预聚体的原料总质量的6%，二月桂酸二丁基锡占用于制备预聚体的原料总质量的0.14%。52.0g (0.23mol) isophorone diisocyanate (IPDI), 58.0g (0.11mol) PCL205u (polycaprolactone diol), 7.0g (0.047mol) dimethylolpropionic acid (DMPA), 0.16g of dibutyltin dilaurate was reacted at 75°C for 4h to prepare a prepolymer. At this time, the molar ratio of the total amount of PCL205u and DMPA to IPDI was 1: 1.465, dimethylolpropionic acid accounted for 6% of the total mass of raw materials used to prepare the prepolymer, and dibutyltin dilaurate accounted for 6% of the total mass of raw materials used to prepare the prepolymer. 0.14% of the total mass of raw materials.
向预聚体中加入11.0g(0.082mol)丙烯酸羟丙酯，70℃反应2h，对预聚体的-NCO进行封端。此时，丙烯酸羟丙酯的摩尔量与预聚体中NCO的摩尔量的投料比为0.35：1。 降温至 40℃，加入4.8g(0..047mol)三乙胺进行中和反应10min生成盐。其中三乙胺的摩尔量与DMPA 的摩尔量相同。 加入去离子水进行乳化 15min，得到可光固化水性聚氨酯乳液。Add 11.0 g (0.082 mol) of hydroxypropyl acrylate to the prepolymer, react at 70°C for 2 hours, and end-cap the -NCO of the prepolymer. At this time, the feeding ratio of the molar amount of hydroxypropyl acrylate to the molar amount of NCO in the prepolymer is 0.35:1. Cool down to 40°C, add 4.8g (0..047mol) triethylamine to carry out neutralization reaction for 10min to form a salt. Wherein the molar weight of triethylamine is the same as that of DMPA. Deionized water was added for emulsification for 15 minutes to obtain a photocurable water-based polyurethane emulsion.
2、有机硅改性正硅酸乙酯预缩合前驱体的制备：2. Preparation of organosilicon-modified ethyl orthosilicate pre-condensation precursor:
同上。Ditto.
3、涂层材料的制备：3. Preparation of coating materials:
将可光固化水性聚氨酯乳液与有机硅改性正硅酸乙酯预缩合前驱体按质量比为1∶3的比例混合，进行UV光固化及进一步缩合聚合后，得到涂层材料。The photocurable water-based polyurethane emulsion is mixed with the organosilicon-modified tetraethyl orthosilicate pre-condensation precursor in a mass ratio of 1:3, and the coating material is obtained after UV light curing and further condensation polymerization.
4、验证产品性能：4. Verify product performance:
将取得的涂层材料，按照GB/T 1743-1979进行光泽度测试，得到涂层光泽度93o；The obtained coating material is subjected to a gloss test according to GB/T 1743-1979, and the coating gloss is 93 ° ;
按照GB 1720-1979进行附着力检测，附着力1级。Adhesion test according to GB 1720-1979, adhesion level 1.
按照GB/T 6739-1996进行硬度检测，硬度为3H。The hardness test is carried out according to GB/T 6739-1996, and the hardness is 3H.
实施例3：Example 3:
1、可光固化水性聚氨酯乳液的制备：1. Preparation of photocurable water-based polyurethane emulsion:
将45.5g(0.20mol)异佛尔酮二异氰酸酯(IPDI)、58.0g(0.11mol) PCL205u（聚己内酯二元醇）、5.5g(0.037mol)二羟甲基丙酸 (DMPA) 、0.11g二月桂酸二丁基锡，在75℃反应4h，制备预聚体。此时PCL205u和 DMPA的总量与IPDI的投料摩尔比为1∶1.36，二羟甲基丙酸占用于制备预聚体的原料总质量的5%，二月桂酸二丁基锡占用于制备预聚体的原料总质量的0.1%。45.5g (0.20mol) isophorone diisocyanate (IPDI), 58.0g (0.11mol) PCL205u (polycaprolactone diol), 5.5g (0.037mol) dimethylolpropionic acid (DMPA), 0.11g of dibutyltin dilaurate was reacted at 75°C for 4h to prepare a prepolymer. At this time, the molar ratio of the total amount of PCL205u and DMPA to IPDI was 1: 1.36, dimethylolpropionic acid accounted for 5% of the total mass of raw materials used to prepare the prepolymer, and dibutyltin dilaurate accounted for 5% of the total mass of raw materials used to prepare the prepolymer. 0.1% of the total mass of raw materials.
向预聚体中加入11.0g(0.072mol)季戊四醇三丙烯酸酯，70℃反应2h，对预聚体的-NCO 进行封端。此时，季戊四醇三丙烯酸酯的摩尔量与预聚体中NCO的摩尔量的投料比为0.1：1。 降温至 40℃，加入3.8g(0..037mol)三乙胺进行中和反应10min生成盐。其中三乙胺的摩尔量与 DMPA 的摩尔量相同。 加入去离子水进行乳化 15min，得到可光固化水性聚氨酯乳液。Add 11.0 g (0.072 mol) of pentaerythritol triacrylate to the prepolymer, react at 70°C for 2 hours, and end-cap the -NCO of the prepolymer. At this time, the feeding ratio of the molar amount of pentaerythritol triacrylate to the molar amount of NCO in the prepolymer is 0.1:1. Cool down to 40°C, add 3.8g (0..037mol) triethylamine to carry out neutralization reaction for 10min to form a salt. The molar amount of triethylamine is the same as that of DMPA. Deionized water was added for emulsification for 15 minutes to obtain a photocurable water-based polyurethane emulsion.
2、有机硅改性正硅酸乙酯预缩合前驱体的制备：2. Preparation of organosilicon-modified ethyl orthosilicate pre-condensation precursor:
同上。Ditto.
3、涂层材料的制备：3. Preparation of coating materials:
将可光固化水性聚氨酯乳液与有机硅改性正硅酸乙酯预缩合前驱体按质量比为1∶2的比例混合，进行UV光固化及进一步缩合聚合后，得到涂层材料。The coating material is obtained by mixing photocurable water-based polyurethane emulsion and organosilicon-modified tetraethyl orthosilicate pre-condensation precursor in a mass ratio of 1:2, performing UV light curing and further condensation polymerization.
4、验证产品性能：4. Verify product performance:
将取得的涂层材料，按照GB/T 1743-1979进行光泽度测试，得到涂层光泽度95o；The obtained coating material is tested for gloss according to GB/T 1743-1979, and the gloss of the coating is 95 ° ;
按照GB 1720-1979进行附着力检测，附着力1级。Adhesion test according to GB 1720-1979, adhesion level 1.
按照GB/T 6739-1996进行硬度检测，硬度为3H。The hardness test is carried out according to GB/T 6739-1996, and the hardness is 3H.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710160316.0A CN106939143B (en) | 2017-03-17 | 2017-03-17 | The preparation method of photocuring aqueous polyurethane-silicon-oxygen-silicon inierpeneirating network structure coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710160316.0A CN106939143B (en) | 2017-03-17 | 2017-03-17 | The preparation method of photocuring aqueous polyurethane-silicon-oxygen-silicon inierpeneirating network structure coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106939143A true CN106939143A (en) | 2017-07-11 |
| CN106939143B CN106939143B (en) | 2019-03-29 |
Family
ID=59469732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710160316.0A Active CN106939143B (en) | 2017-03-17 | 2017-03-17 | The preparation method of photocuring aqueous polyurethane-silicon-oxygen-silicon inierpeneirating network structure coating material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106939143B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148171A (en) * | 2017-12-11 | 2018-06-12 | 湖北大学 | A kind of hydrolysis-resistant waterborne polyurethane dispersion and preparation method thereof |
| CN111560204A (en) * | 2020-06-15 | 2020-08-21 | 李艳艳 | Self-repairable polycarbonate surface antifogging coating and preparation method thereof |
| CN112119353A (en) * | 2018-02-09 | 2020-12-22 | 联合富大有限公司 | photosensitive adhesive |
| CN113416280A (en) * | 2021-05-28 | 2021-09-21 | 华南理工大学 | Ultraviolet-cured silicon-containing organic-inorganic hybrid resin and preparation method thereof |
| CN113637137A (en) * | 2021-07-22 | 2021-11-12 | 昆山优瑞森医疗科技有限公司 | Preparation method of synthetic siloxane polyurethane copolymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735599A (en) * | 2009-12-24 | 2010-06-16 | 华南理工大学 | Ultraviolet curing organic silicon modified polyurethane aqueous dispersoid and preparation method thereof |
| CN103709927A (en) * | 2013-12-04 | 2014-04-09 | 江南大学 | Preparation method for antifogging thin film coating with high light transmission |
-
2017
- 2017-03-17 CN CN201710160316.0A patent/CN106939143B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735599A (en) * | 2009-12-24 | 2010-06-16 | 华南理工大学 | Ultraviolet curing organic silicon modified polyurethane aqueous dispersoid and preparation method thereof |
| CN103709927A (en) * | 2013-12-04 | 2014-04-09 | 江南大学 | Preparation method for antifogging thin film coating with high light transmission |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148171A (en) * | 2017-12-11 | 2018-06-12 | 湖北大学 | A kind of hydrolysis-resistant waterborne polyurethane dispersion and preparation method thereof |
| CN108148171B (en) * | 2017-12-11 | 2020-10-30 | 湖北大学 | Hydrolysis-resistant aqueous polyurethane dispersion and preparation method thereof |
| CN112119353A (en) * | 2018-02-09 | 2020-12-22 | 联合富大有限公司 | photosensitive adhesive |
| CN111560204A (en) * | 2020-06-15 | 2020-08-21 | 李艳艳 | Self-repairable polycarbonate surface antifogging coating and preparation method thereof |
| CN113416280A (en) * | 2021-05-28 | 2021-09-21 | 华南理工大学 | Ultraviolet-cured silicon-containing organic-inorganic hybrid resin and preparation method thereof |
| CN113637137A (en) * | 2021-07-22 | 2021-11-12 | 昆山优瑞森医疗科技有限公司 | Preparation method of synthetic siloxane polyurethane copolymer |
| CN113637137B (en) * | 2021-07-22 | 2023-06-06 | 昆山优瑞森医疗科技有限公司 | Preparation method of synthetic siloxane polyurethane copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106939143B (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106939143A (en) | The preparation method of photocuring aqueous polyurethane silica silicon inierpeneirating network structure coating material | |
| CN100424145C (en) | UV-curable waterborne polyurethane acrylate coating resin and preparation method thereof | |
| CN102070768B (en) | Water-soluble polyurethane for wood lacquer and preparation method thereof | |
| CN110352204B (en) | Aqueous coating composition | |
| JP3885531B2 (en) | Water-based polyurethane emulsion, water-based adhesive and water-based paint using the same | |
| CN103080164A (en) | Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor | |
| CN103588951B (en) | A kind of preparation of high-strength hydrophobicity photocuring aqueous polyurethane nano composite emulsion | |
| CN102863829A (en) | Humidity and ultraviolet dual-cured polyurethane woodware coating and preparation method thereof | |
| CN101235148A (en) | Multi-crosslinked UV-curable aqueous polyurethane dispersion and its preparation method and application | |
| TW200408678A (en) | Radiation-curable polyurethane dispersion | |
| JP6165419B2 (en) | Aqueous two-component coating composition, ink composition, adhesive composition, and method of using the same | |
| CN106634525A (en) | A kind of polyurethane acrylate cathodic electrophoretic coating and its preparation method and application | |
| TWI655244B (en) | Radiation-curable aqueous composition having controlled polymer flow and preparation method thereof | |
| CA2607274A1 (en) | Radiation curable polyurethane dispersions | |
| CN109054623A (en) | Photo-curing polyurethane acrylate aqueous dispersion and preparation method thereof | |
| JP2002537454A5 (en) | ||
| US20150111978A1 (en) | Method of forming dual curable polymer compositions | |
| CN104698754B (en) | A kind of photoetching compositions prepared based on PCDL type polyurethane acrylate | |
| CN110669202A (en) | Light-curable aqueous hyperbranched resin and preparation method thereof | |
| CN106632968A (en) | Preparation method of fluorosilicone modified waterborne UV cured hyperbranched brush polyurethane | |
| CN103333318A (en) | Preparation method of polyurea acrylic ester | |
| JP2006022133A (en) | Aqueous polyurethane emulsion, production method thereof and use thereof | |
| CN105885010A (en) | Preparation method of high-activity water-based UV-curing fluororesin | |
| JP2001151847A (en) | Printing ink binder and printing ink | |
| CN118440582B (en) | Coating compositions, materials, kits and methods of use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |